Emulsifiable insecticide compositions



United States Patent Ofiice 2,862,848 EMULSIFIABLE, INSECTICIDECOMPOSITIONS Vincent J. Keenan, Ardmore',Pa., assignor to The AtlanticRefining Company, Philadelphia, Pa., a corporation of Pennsylvania V H aNo Drawing. 1 Application September21, 1955 Serial No. 535,754

12. Claims. (Cl. 167 42) This invention relates to an emulsifiableinsecticide composition and, more particularly, to an emulsifiableinsecticide composition wherein the insecticide soluble in aromatichydrocarbons and wherein the emulsifiable agent is a particular ammoniumsalt of an alkyl aryl sulfonic acid or mixtures of alkyl aryl sulfonicacids, wherein the alkyl group contains 12 carbon atoms or averages 12carbon atoms, respectively. 7

This application is a continuation-in-part of Vincent J. Keenanapplication Serial No. 249,807, filed October. 4',

1951, now abandoned, and entitled Emulsifiable Insectisolubleinsecticides in water to obtain the necessary dilution.

A number of emulsifying agents have been utilized for this purpose,however, in general, these emulsifying agents have been suitable onlyfor producing emulsions having a rather short time of stability,generally from /2 to 2 hours. Inasmuch as it is desirable when sprayinglarge'orchards or large acreages of crops to make up a batch of emulsionin suflicient quantity .to last for an entire day or, in certaininstances, even overnight so that the batch may be utilized in the nextdays operations, an emulsifying agent is necessary which will produce anemulsion stable for about 24 hours. Furthermore, those emulsions whichhave only a short time of stability will usually show a tendency topartially break in a very short time with the result that an unevenconcentration of insecticide in the spray is produced, therebyover-treating and under-treating various portions of the same field. Theemulsions should not be completely stable, however, since if they arecompletely stable the first rain that comes after application will washoif the insecticide. In this connection, Dr. A. W. A. Brown in his bookInsect Control by Chemicals, John Wiley and Sons, Inc.,*New* 2 York'(1951), at page 55 states: It has been concluded that coarse,quick-breaking emulsions are superior,

since the water quickly runs ofl without taking the oil with it, butinstead leaves it as a continuous film. Similarly, Dr. Donald E. H.Frear in his book Chemistry of the Pesticides, D. Van Nostrand Co., Inc.(1955), points out on page 420 that a number of Workers have studied thefactors which aflect the deposition of oil from oil emulsion sprays andhave shown that as far as the deposit is concerned a quick breakingemulsion is betterthan-one I more stable.

It is an object of this invention to produce an emulsi fiableinsecticide composition of an aromatic hydrocarbon soluble insecticidewhich is stable for about 24 hours.

It is a further object of this invention to produce an emulsifiableinsecticide composition of an aromatic hydrocarbon soluble insecticidewhich has little tendency to partially break during its period ofstability.

In accordance with this invention, insecticides such as DDT(2,2-bis(p-chlorophenyl) 1,1,1 trichloroethane),

DDD (2,2-bis (p-chlorophenyl) -1, l-dichloroethane, DFDT I (2,2-bis(p-fluorophenyl) 1,1,1- trichloroethane) DMDT(2,2-bis(p-methylphenyl)-l,l,l trichloroethane), Methoxychlor (2,2-bis(p-methoxyphenyl) 1,l,l-trichlOroethane), Toxaphene (chlorinatedcamphene; C H Cl Chlo rdane (not less than 60% ofl,2,4,5,6,7,8,8-octachlo- 'ro-4,7-methano-3a,4,7,7a-tetrahydroindane,with the re- It has therefore been 7 found necessary to emulsify thesearomatic hydrocarbon mainder being related dicyclopentadienederivatives);

Heptachlor (C H Cl Benzene Hexachloride (hexachlorocyclohexane) Aldrin(1,2,3,4,10,10-hexachloro-1:4, 5 S-diendomethano-l,4,4a,5,8,8ahexahydronaphthalene),

quently sulfonated to produce the desired sulfonic acids 7 may beprepared by a variety of methods, for example, bythe alkylation of anaromatic hydrocarbon with a branch chain olefin having preferably 12carbon atoms in the presence of a catalyst, such as AlC1 HF, H BF orsimilar acid type catalysts. The olefin may be obtained from thepolymerization of propylene over phosphoric acid or similar catalysts,by the polymerization of butylenes, etc. However, since thepolymerization reaction produces a mixture of compounds including thosehaving molecular weights both in excess of and less than those desired,such mixtures must be separated to obtain only those polymers which fallwithin the C to C range. total product in order to obtain a mixture ofolefins wherein the average molecular weight is in the C range and onlyvery small amounts of olefins are present out-1 side the C to C range.The aromatic employed may be benzene, toluene, or any one of theisomeric xylenes or mixtures of such isomers, ethyl benzene,propyl-benzene, and similar lower alkyl aromatics.-

l' 'a t ented Dec. 2, 1958 In other words, a heart cut is taken from theA third method of preparationiofthe alkyl aromatics employs achlorinated hydrocarbon having 11 to 13 carbon atoms reacted with thearomatic hydrocarbon in the presence of a Friedel-Crafts catalyst suchas A101 The alkyl halide may be conveniently obtained by chlorinatingthe proper petroleum fraction, such as a kerosine fraction. Thearomatics suitable in the previous examples are likewise suitable inthis method.

Specific examples of the alkyl aromatic hydrocarbons herein contemplatedas suitable for the invention are undecyl benzene, undecyl toluene,undecyl ethyl benzene, undecyl dimethyl benzene, undecyl diethylbenzene, undecyl methyl ethyl benzene, undecyl methyl propyl benzene,undecyl dipropyl benzene, dodecyl benzene, dodecyl toluene, dodecylethyl benzene, dodecyl propyl benzene, dodecyl dimethyl benzene, dodecyldiethyl benzene, dodecyl methyl ethyl benzene, dodecyl methyl propylbenzene, dodecyl dipropyl benzene, tridecyl benzene, tridecyl toluene,tridecyl ethyl benzene, tridecyl propyl benzene, tridecyl dimethylbenzene, tridecyl diethyl benzene, tridecyl methyl ethyl benzene,tridecyl methyl propyl benzene, tridecyl dipropyl benzene. The abovenamed alkyl aromatic hydrocarbons or mixtures thereof may be sulfonatedaccording to conventional methods, utilizing concentrated (98%) sulfuricacid or fuming sulfuric acid. a

The foregoing methods of preparing the desired sulfonic acids aredescribed in detail in United States Patent No. 2,615,847 and in thereferences enumerated therein.

The sulfonic acids thus produced may be neutralized by any one of thefollowing organic amines or organic quaternary ammonium compounds:morpholine, pyridine, picoline, trialkanol amines, wherein the alkanolgroup may contain from 2 to 4 carbon atoms, dialkyl alkanol amineswherein the alkyl groups and alkanol group may contain from 2 to 4carbon atoms, and tetra alkyl ammonium hydroxide wherein the alkylgroups may contain from 2 to 4 carbon atoms.

It will be apparent from the tables of data which follow that only theabove specific ammonium salts of the specific sulfonic acids set forthare suitable as emulsifying agents for the various aromatic hydrocarbonsoluble insecticides of the type also enumerated above.

The following examples are presented in order to illustrate specificaspects of the present invention; these examples, however, should not beconstrued as limiting the invention thereto.

A gas stream comprising about 80 percent propylene with minor amounts ofpropane, ethane, ethylene and methane was contacted with a catalystconsisting of phosphoric acid impregnated on kieselguhr at a temperatureof 500 F. to 550 F. and 400 p. s. i. pressure, at a rate of about 0.1pound mols of propylene per pound of catalyst per hour. The resultingmixture of propylene polymers containing from 6 to 18 carbon atoms andboiling between 300 F. and about 520 F. was fractionally distilled toremove an overhead fraction boiling between approximately 300 F. and 340to 360 F. comprising mainly the trimers, i. e. polymers containing 9carbon 4 atoms, a second cut boiling up to approximately 465 F. andcomprising predominantly tetramers (C polymers), leaving a distillationresidue or bottoms boiling up to about 520 F. comprising the pentamersor C polymers. Each of these fractions was admixed separately with about6 molar equivalents of benzene and each mixture treated with an aluminumchloride catalyst at about 140 F. to 150 F. to effect alkylation of thebenzene with the propylene polymers. The spent catalyst was separated bysettling and the crude alkylate was neutralized with caustic sodasolution and then washed with water. The washed crude alkylate was thenfractionally distilled to remove excess benzene and alkyl benzenesboiling outside of the desired ranges. In the case of the alkylateproduced from the C polymer fraction the monoalkyl benzenes boilingbetween about 400 F. and 500 F. were separated. In the case of Cmonoalkyl benzenes a fraction boiling between about 500 F. and 630 F.was separated and in the case of the C monoalkylated benzene a fractionboiling between about 550 F. and 680 F. was separated. In each'case onevolume of the alkylated benzene hydrocarbon was contacted with onevolume of 98 percent concentration sulfuric acid at about 150 F. forabout 30 minutes to produce the monosulfonic acid. The sulfonationreaction mixture was then diluted with about 6 volumes of benzene andpermitted to settle and stratify into an upper layer comprising benzenecontaining the hydrocarbon sulfonic acids with only minor amounts ofunsulfonatedhydrocarbons and entrained sul- ;fonic acid. 1 This was thenseparated from the lower layer containing the spent sulfonic acid.

Seven volumes of the benzene solution of the sulfonic acids was mixedwith 4 volumes of 50 percent aqueous methanol. The mixture was stirredand permitted to set- "tle for about ten minutes.

- desired organic amine of organic quaternary ammonium compound of thetypes mentioned hereinbefore were added. The amount added was sufficientto raise the pH of the solution to 7. This solution was then evaporatedto a solids content ranging between 40 to 50 percent by weight. To onevolume of the evaporated solution was added 15 volumes of Xylene and themixture distilled to azeotrope off the water and small amounts ofalcohol and benzene thus producing a xylene solution of the sulfonate.

The C C and C alkyl benzene sulfonic acids prepared as described abovewere separately neutralized with triethanol amine by the foregoingprocedure. These salts were used as emulsifying agents and compared witheach other and with the triethanol amine salt of a C (lauryl) alcoholsulfate. The results of these experiments are set forth in Table Iwherein it will be seen that concentrated solutions of DDT, emulsifyingagent, and xylene were prepared and thereafter emulsified with Water inthe proportions shown and observations taken after 30 minutes and after24 hours with regard to the stability of the emulsion.

It is to be noted in the tables of data which follow that theconcentration to which the sulfonate solution is reduced by evaporationor other means is not critical since the concentration of sulfonate inthe mixture is expressed as percent by Weight of the active sulfonatecompound.

ass s is Triethanol ammonium salts as emulsifying agents Emulsion: 1Vol. of Concentrate Emulsion: 1 Vol. of Conontrate f I and 1 Vol. ofHard Water and 2 Vols. of Hard Water Concentrates Composition(Percentage byWeight) Condition After Conditiom "Condition After.Condition 30 Minutes After 30 Minutes After 24 Hours 24 Hours PartiallyStable Partnu some...

65% Xylene (in (Tn' Broken do Broken Stable Sfiah'l Stable 30% DDT 3%012" Alkyl Benzene Sulfnnate do 67% Xylene 30% DDT 3% On Alkyl BenzeneSulfrmato do do 9. 67% Xylene 3% DDT 2 012" Alkyl Benzene Sulfonetedo dol i V 68% Xylene :i u' z 5 :5. i DDT 1% C1 Alkyl Benzene Sulfonate-Partially Stable Broken.' Broken; 69% Xylene 30% DDT "'1" '1 h. 5% 09"Alkyl Benzene Sulfflflata }Stable Siam The table shows that only the Calkyl benzene "ities when'va rious organic compounds (selected as beingfonate emulsions were stable at the end of 24 hours.

In Table H there is presented the results of similar experiments whichwere conducted to compare a C alkyl benzene sulfonic acid neutralizedwith caustic (so.- dium hydroxide) and the C alkyl benzene sulfonic acidneutralized with triethauol amine.

The C alkyl benzene sulfonic acid was prepared as described in theexample for Table I. One portion was neutralized with triethanol amineas described forthat example of Table I. A second portion of the C alkylbenzene sulfonic acid solution in the aqueous methanol was neutralizedto a pH of about7 with a 25% .con-

representative of a large group of compounds tried) were..utilized.-asneutralization agents" for. the sulfonic acid to demonstrate thespecificity of theparticular com-, 7

pounds hereinbefore enumerated as being suitable.

' Inea'ch' case'the' C alkyl b enzene sulfonic acid was prepared asdescribed in the example preceding Table I 'Nand neutralized.accordinglfttilthe' lte'jchniques described centration aqueous"sodiumhydroxide solution. This solution about and percen weight;

TABLEII I of Concentrate and 1 Concentrates Composition {Percentage byWeight). 3 ;1: 1,. Condition- V V Condition LY 1 After 30. Aiter24 ml 1Min ts 11 30% DD Partially.

5% Triethanol -Ammon1um Cm" Alkyl Benzene Sulfonate: i t.

/ Yol. of Hard Waten v as then'evaporat'ed to a solids c'ontent rangingly ineiiective as an emulsifying agent for,these.-insecticides. 7Similarly, other inorganic neutralization. agents werefoundto beinefiective.;

In Table III the results are given for emul on stabil in connection withsuch example:

Table I11 Compositionbf concentrates .30%(W t.) DDT- a 1.5% (wt.)emulsifying agent. I

68.5% (wt;) xylene. u 1 v One volume of eoncentrate added to one volumeof hard water and emulsified.

CompoundUsed to Neutralize the Ou'Alkyl Condition Condition BenzeneSulfon io Acid to Prepare the Emulof Emulsion of Emulsion sifying AgentAfter 30 After 24 .Minutes Hours.-

AmmoniumHydroidde- 'i-- Broken. TetraethylAmmonium Hydroxide Stable.Isopropylamine; Broken. emember- 2, Amino; 1, Birtanol. Do.

MonoethanolAmine o Do. ButylDietlian'ol A'min Brokenm; Do.Trimethyl'Aminese. Stable... Partially Broken Morpholine Diethyl EthanolAmine .do Arnyl Diethanol Amine Broken Broken 3 Isopropoxy PropylAminel. o Do.

This table shows that the sodlum sulfonate 1s entire. s i i V In TableIV a comparison is made of the emulsification tprjopperties of. various,mixtures'of trieth'anol ammoniuni alkyl}benzenelsultonateswith thesodium soap of alien soluble petroleum sulfonic acid extracted from theproduct obtained by the acid treatment of medicinal white oils.

TABLE-Iv? 8 A concentrate was prepared'by combining a 2.9 percent bywei'ghtjofthe triethanolamine ol'eate, 0.1 percent Blends f triethanolammonium C alkyl benzene-sulfonate and sodium salts of ptroleumwhitelfioil sulfonicf acids Emulsion: 1 Volume of Emulsion: 1 Volume ofConcentrate and 1 Concentrate and 2 Volume of Hard Water Volumesot HardWater Concentrates Composition Condition Atter Condition Afterso Mine.24 Hrs. 30 Mins. 24 Hrs. I

30% DDT 5% {75% C Sulfonate Stable. Stable... Stable..." Stable.

% Sodium Sultonate...

s% {75% dii'siz'ffiiifiik do (in do Do,

25% Sodium Sultanate...

67g, lgllsl efne 1% 75% 0,, Snlfnnata dn do Brokenm. Broken.

25% Sodium Sulfonate.-.

5 {5 o Silltnnatp do do Stable Partially Sodium S111t'onate. r 7 Stable.

3% {50% Cu Su1tonate do Brokenm- BrokenL... Broken.

50% Sodium Sultana I% {5O% CiiSii ltonat Br do Do.

50% Sodium Sulfonetm;

3 25% drain-rm..- do n m. Do.

75% Sodium Sultonote 1% 25 drain-nan; Beam an do. Do, 75% SodiumSultonate 69% Xylene This table shows that the petroleum sulfonate byitself is entirely unsuitable as an emulsifying ,agent. Furthermore,these results also show that the alkyl benzene sulfonate cannot be mixedwith more than 25 percent of the petroleum sultonate without seriouslydecreasing the stability of the emulsion. V

A concentrate was produced by combining 2.2 percent by weight of thetriethanolamine salt of the C alkyl benzene sul'fonic .acid, 0.4 percentby weight of a petroleum white oil, 0.4 percent by weight of the sodiumsalt of 7 xylene, and 30 percent by weight DDT. This concentrate wasthen mixed with water in a ratio of 1 part by weight of concentrate to 5parts by weight of water to produce an emulsion. V The emulsion brokecompletely in 10 minutes, showing that oleic acid cannot be substitutedfor the C alkyl benzene. sulfonic acid to produce tri ethanolarninesaltswhich will give stable emulsions.

by weight white oil, .67 percent by weight xylene, and 30 percent byweight DDT. This concentrate was then mixed with water in .a ratio of, Ipart by weight of concentrate to 5 parts by weight of water to producean emulsion. This emulsion broke within 10 minutes, thus showing thatthe addition of White oil to the triethanolamine oleate does not give astable -emulsion.

A concentrate was prepared by combining 3 percent by weight of thetriethanolamine salt of a white oil sulfonate, 67 percent by weightxylene, and 30 percent by weight DDT. This concentrate was then mixedwith water in a ratio of 1 part by weight of concentrate to 5 parts byweight of water to produce an emulsion. This emulsion broke within 30minutes, thus demonstrating that neither the triethanol'amine salt northe sodium salt (Table IV) of white oil sulfonic acids are suitable forstable emulsions.

The above data have all been directed to the emulsification of theparticular insecticide DDT, purely for purposes of comparison of thevarious emulsification agents. In Table V which follows, data arepresented on other insecticides demonstrating the applicability of thepreferred emulsifying agents to other aromatic hydrocarbon solubleinsecticides. Inthese experiments the concentrate was diluted withsufficient water to give the various percentages of insecticide 'in'theemulsion as noted. In each experiment the triethanol ammonium C 5 alkylbenzene-sulfo- 9 V nate of the example of Table I was used as theemulsifying agent.

vent selected from the TABLE v 15% Emulsion 12.5% Emulsion 10% Emulsion5% Emulsion Concentrates a Composition (Percentage by nd. Atter- 00nd.After- Cond. Mter- Cond. After- Weight) 30 Mine. 24 Hrs. 30 Mins. 24Hrs. 30 Mins. 24 Hrs. 30 Mine. 24 Hrs.

30% Toxaphene Stable S l Stable... Stable.-. Stable.-. Stable.

} do do do do do 7 Do u do do do do do Do,

do do Brokem. Broken- Broken.

Partially Stable.

Stable... Stable Stable... Stable.

do do do Do.

Partially do do do 72% Xylene Stable. 62% Chlordane f z gfi gf f fStable... Stable".-. 18% Kerosina- 62%EChlodanie in. gen 6% Xylene- 23%Kerosine 62% Chlordane Em. Agent Partially Br k n 3 3% Xylene Stable.29.7% Kerosine The insecticides of this invention in addition to beingaromatic hydrocarbon soluble may also be characterized as being halogencontaining compounds. The various naturally occurring vegetableinsecticides such as nicotine, pyrethrins, rotenone, and like compunds,are not included within the scope of this invention since such compoundsare generally insoluble in aromatic hydrocarbons and are applied asdusts, or as in the case of nicotine in true water solutions.

In preparing the emulsifiable insecticide composition of this invention,the insecticide is first dissolved in the proper amount of aromatichydrocarbon, such as xylene or methyl-naphthalene. The ammonium salt ofthe C alkyl benzene sulfonates of this invention are produced in aqueoussolution which is mixed with xylene and the mixture distilled to producean overhead azeotropic mixture of xylene and water. the water is removedand a xylene solution of the salt remains and may then be mixed with theXylene solution of the insecticide to produce the concentrate.Generally, the amount of salt based upon the total weight of concentratemay vary from 0.5 per cent to percent, however, from 1. percent to 5percent is preferred. The concentration of the insecticide may rangefrom 10 percent to 40 percent, generally, and preferably from percent topercent by weight of the concentrate. Obviously, these percentages mayvary due to the solubility of the insecticide and of the ammonium saltsand in accordance with the desired concentration of insecticide in theemulsion to be used on the crops.

I claim:

1. A water emulsifiable insecticide composition consisting essentiallyof from 10 percent to 40 percent by weight of a xylene solubleinsecticide, from 50 percent to This is continued until all ofconsistingof morpholinium, pyridinium, picolinium, trialkanol ammonium, dialkylalkanol ammonium, and tetra-alkyl ammonium, wherein the alkanol andalkyl groups contain from 2 to 4 carbon atoms.

2. The composition according to claim 1 wherein the salt is themorpholiniurn salt.

3. The composition according to claim 1 wherein the salt is thepyridinium salt.

4. The composition according to claim 1 wherein the salt is thetriethanol ammonium salt.

5. The composition according to claim 1 wherein the salt is the diethylethanol ammonium salt.

6. The composition according to claim 1 wherein the salt is thetetraethyl ammonium salt.

7. A water emulsifiable insecticide composition consisting essentiallyof from 10 percent to 40 percent by Weight of a xylene solubleinsecticide, from 50 percent to 89.5 percent by weight of an aromatichydrocarbon solvent selected from the group consisting of benzene,toluene, xylene, higher alkylated aromatic hydrocarbons and methylnaphthalene, and from 0.5 percent to 10 percent by weight of a salt ofan alkyl benzene monosulfonic acid, wherein the alkyl group contains 12carbon atoms, said salt being selected from the group consisting ofmorpholinium, pyridinium, picolinium, trialkanol ammonium, dialkylalkanol ammonium, and tetra-alkyl ammonium, wherein the alkanol andalkyl groups contain 89.5 percent by weight of an aromatic hydrocarbonsolfrom 2 to 4 carbon atoms.

group consisting .of benzene; toluene, xylene, higher alkylated aromatichydrocarbons 8. The composition according to claim 7 wherein the saltis'themorpholinium salt. I

9. The" composition according to claim 7- wherein the salt is pyridiniumsalt. 2,447,475 10. The composition according to claim 7 wherein the 52552187 salt is triethanol ammonium salt. v y H I p 11. The compositionaccording toc'lair'n 7 Whereimth'e 710 415 salt is diethyl ethanolammonium salt. I v V 12. The composition according to claim 7 Whereinthsalt is tetraethyl ammonium salt. V '10 References Cited in the file ofthis patent UNITED STATES PATENTS Kaberg Aug. 17, 1 948 QIKosmin May 8,1951 FOREIGNPATENTS France June 8, 1931

1. A WATER EMULSIFIABLE INSECTICIDE COMPOSITION CONSISTING ESSENTIALLYOF FROM 10 PERCENT TO 40PERCENT BY WEIGHT OF A XYLENE SOLUBLEINSECTICIDE, FROM 50 PERCENT TO 89.5 PERCENT BY WEIGHT OF AN AROMATICHYDROCARBON SOLVENT SELECTED FROM THE GROUP CONSISTING OF BENZENE,TOLUENE, XYLENE, HIGHER ALKYLATED AROMATIC HYDROCARBONS AND METHYLNAPHTHALENE, AND FROM 0.5 PERCENT TO 10 PERCENT BY WEIGHT OF A SALT OF AMIXTURE OF ALKYL BENZENE MONOSULFONIC ACIDS WHIEREIN THE SUM OF THECARBON ATOMS IN THE ALKYL GROUPS ATTACHED TO EACH BENZENE RING RANGESBETWEEN 11 TO 19, EACH BENZENE RING HAVING ONE ALKYL GROUP ATTACHEDTHERETO RANGING BETWEEN 11 AND 13 CARBON ATOMS IN LENGTH, SAID SALTBEING SELECTED FROM THE GROUP CONSISTING OF MORPHOLINIUM, PYRIDINIM,PICOLINIUM, TRIALKANOL AMMONIUM, DIALKYL ALKANOL AMMONIUM, ANDTETRA-ALKYL AMMONIUM, WHEREIN THE ALKANOL AND ALKYL GROUPS CONTAIN FROM2 TO 4 CARBON ATOMS.